Metallocenes containing aryl-substituted indenyl derivatives as ligands, process for their preparation, and their use as catalysts

Abstract

A very effective catalyst system for the polymerization or copolymerization of olefins comprises a cocatalyst, preferably an aluminoxane or a supported aluminoxane, and a metallocene of the formula I in which, in the preferred form, M 1 is Zr or Hf, R 1 and R 2 are halogen or alkyl, R 3 is alkyl, R 4 to R 12 are alkyl or hydrogen and R 13 is a (substituted) alkylene or heteroatom bridge. The metallocenes, in particular the zirconocenes, produce polymers of a very high molecular weight, in the case of prochiral monomers polymers of a very high molecular weight, very high stereoactivity and very high melting point, at high catalyst activities in the industrially particularly interesting temperature range between 50 and 80° C. In addition, reactor deposits are avoided by means of supported catalyst systems.

What is claimed is:  
     
       1. A compound of formula I:                    
       in which 
       M 1  is a metal from group IVb, Vb or VIb of the Periodic Table,  
       R 1  and R 2  are identical or different and are a hydrogen atom, a C 1 -C 10 -alkyl group, a C 1 -C 10 -alkoxy group, a C 6 -C 10 -aryl group, a C 6 -C 10 -aryloxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 40 -arylalkyl group, a C 7 -C 40 -alkylaryl group, a C 8 -C 40 -arylalkenyl group, an OH group or a halogen atom,  
       the radicals R 3  are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 -alkyl group, which may be halogenated, a C 6 -C 10 -aryl group, an —NR 16   2 , —SR 16 , —OSiR 16   3 , —SiR 16   3  or —PR 16   2  radical, in which R 16  is a halogen atom, a C 1 -C 10 -alkyl group or a C 6 -C 10 -aryl group,  
       R 4  to R 12  are identical or different and are as defined for R 3 , or adjacent radicals R 4  to R 12 , together with the atoms connecting them, form one or more aromatic or aliphatic rings, or the radicals R 5  and R 8  or R 12 , together with the atoms connecting them, form an aromatic or aliphatic ring,  
       R 13  is                    
       ═BR 14 , ═AIR 14 , —Ge—, —O—, —S—, ═SO, ═SO 2 , ═NR 14 , ═CO,  
       ═PR 14  or ═P(O)R 14 , where R 14  and R 15  are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 -alkyl group, a C 1 -C 10 -fluoroalkyl group, a C 1 -C 10 -alkoxy group, a C 6 -C 10 -aryl group, a C 6 -C 10 -fluoroaryl group, a C 6 -C 10 -aryloxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 40 -arylalkyl group, a C 7 -C 40 -alkylaryl group or a C 8 -C 40 -arylalkenyl group, or R 14 and R 15 , in each case together with atoms connecting them, form one or more rings, and  
       M 2  is silicon, germanium or tin.  
     
     
       2. The compound as claimed in claim  1 , wherein R 3  is C 1 -C 4 -alkyl, R 8  to R 12  are identical or different and are a hydrogen atom or adjacent radicals R 8  to R 12 , together with the atoms connecting them form an aromatic ring, R 1  and R 2  are each a halogen atom, M 1  is zirconium or hafnium and R 13  is                    
       wherein M 2  is silicon and R 14  and R 15  are identical and are a C 1 -C 4 -alkyl.  
     
     
       3. The compound as claimed in claim  2 , wherein R 14  and R 15  are a C 1 -alkyl, and R 1  and R 2  are each a chlorine atom. 
     
     
       4. The compound as claimed in claim  1  wherein, M 1  is titanium, R 1  and R 2  are chlorine, R 4  through R 12  are a hydrogen atom, R 3  is a C 1 -C 4 -alkyl group, R 13  is Si(CH 3 ) 2 . 
     
     
       5. A compound of the formula I as claimed in claim  1 , wherein, in the formula I, M 1  is zirconium or hafnium, 
       R 1  and R 2  are identical and are a C 1 -C 3 -alkyl group or a halogen atom,  
       the radicals R 3  are identical and are a C 1 -C 4 -alkyl group,  
       R 4  to R 12  are identical or different and are hydrogen or a C 1 -C 4 -alkyl group, and  
       R 13  is                    
       where M 2  is silicon or germanium and R 14  and R 15  are identical or different and are a C 1 -C 4 -alkyl group or a C 6 -C 10 -aryl group.  
     
     
       6. A compound of the formula I as claimed in claim  1 , wherein, in the formula I, 
       R 4  and R 7  are hydrogen, and  
       R 5 , R 6  and R 8  to R 12  are identical or different and are hydrogen or a C 1 -C 4 -alkyl group.  
     
     
       7. A compound of the formula I as claimed in claim  1 , wherein, in formula I, M 1  is zirconium, 
       R 1  and R 2  are identical and are chlorine,  
       the radicals R 3  are identical and are a C 1 -C 4 -alkyl group,  
       R 4  and R 7  are hydrogen,  
       R 5 , R 6  and R 8  to R 12  are identical or different and are a C 1 -C 4 -alkyl group or hydrogen, and  
       R 13  is                    
       where M 2  is silicon and R 14  and R 15  are identical or different and are a C 1 -C 4 -alkyl group or a C 6 -C 10 -aryl group.  
     
     
       8. The compound as claimed in claim  1 , wherein said compound is racemic.